Atmospheric water harvesting (AWH) addresses freshwater scarcity, but most sorbents struggle with trade-offs between high moisture uptake, rapid desorption and low-energy regeneration. Herein, a multiscale composite is developed, integrating vertically aligned delignified wood (DW) microchannels, microporous MOF-801 domains, and a thermoresponsive poly (N-isopropylacrylamide)-MXene (PNIPAM-MXene) interface via interfacial synergy. The PNIPAM-MXene interface works dually, MXene's high photothermal efficiency raises local temperature under solar light to trigger PNIPAM's entropy-driven phase transition. This synergy switches wettability from hydrophilic to hydrophobic for water release, breaks water-matrix hydrogen bonds, and reduces desorption activation energy by similar to 19%. Under humid conditions, the composite has a water uptake of 0.82 g.g(-1), and releases similar to 93.9% of absorbed water under simulated solar irradiation. Molecular simulations confirm PNIPAM's entropy-driven transition disrupts interfacial hydrogen bonds, promoting confined water expulsion. This strategy enables low-energy solar-driven AWH, with scalable potential for off-grid water production in arid regions, offering insights for designing multifunctional sorbents bridging high capacity and easy regeneration.